Hello,
I am attempting to optimize an excited state by applying the following parameters:
STATE_FOLLOW TRUE
FOLLOW_ENERGY 1000000
FOLLOW_OVERLAP 90
I chose this set to ensure that the state will not change during optimization. However, in the output, Q-Chem does not seem to consider FOLLOW_OVERLAP=90 and unexpectedly follows the energy as usual. In the output, it mentions that dynamic thresholds are being used to change the set FOLLOW_ENERGY and FOLLOW_OVERLAP. My question is, why does not Q-Chem consider my setting for FOLLOW_OVERLAP=90, and how can I fix this problem?
A part of output:
Step: 1 State: 28
Previous State: 28 -1578.671124720782
Estimated State: -1578.639342681677
Energy threshold: 1.00000 Overlap threshold: 0.900
---------------------------------------------------
State | Energy (Eh) | Delta E (Eh) | Overlap
---------------------------------------------------
12 | -1578.69154355 | -0.052201 | 0.420332
20 | -1578.67887588 | -0.039533 | 0.788062
21 | -1578.67768797 | -0.038345 | 0.825723
22 | -1578.67486410 | -0.035521 | 0.677087
23 | -1578.67468462 | -0.035342 | 0.628466
24 | -1578.67420352 | -0.034861 | 0.759117
25 | -1578.67287486 | -0.033532 | 0.657837
27 | -1578.67191557 | -0.032573 | 0.717409
28 | -1578.67182327 | -0.032481 | 0.717096
34 | -1578.66810992 | -0.028767 | 0.449957
35 | -1578.66764499 | -0.028302 | 0.469805
37 | -1578.66540533 | -0.026063 | 0.556848
40 | -1578.66299332 | -0.023651 | 0.439768
WARNING!!! Character may have changed, choosing by energy
---------------------------------------------------
Switching to state: 40 from 28
Trace of A+D (Beta): 1.9186
Trace of A+D (Alpha): 0.0814
---------------------------------------------------
Stored State: 40 -1578.66299332
---------------------------------------------------
Dynamic thresholds being used
to change set FOLLOW_ENERGY and FOLLOW_OVERLAP
---------------------------------------------------
SETman timing summary (seconds)
CPU time 153708.99s
System time 0.22s
Wall time 6402.03s
Here it should select:
21 | -1578.67768797 | -0.038345 | 0.825723
with the highest overlap.
The input:
$molecule
3 2
Ru 0.00133100 -0.00306100 -0.00037000
C 2.68266900 -1.11322700 -0.56646800
C 2.18752300 0.64165700 -2.03124400
C 3.40396000 0.49660800 -2.67819600
C 4.28145700 -0.48596400 -2.23727800
C 3.91936900 -1.29825200 -1.17080400
C 2.18777100 -1.91651300 0.55492700
C 0.39504400 -2.26304000 2.01607400
C 1.06543800 -3.29099800 2.65861700
C 2.33723300 -3.63515400 2.21822700
C 2.90469500 -2.94323800 1.15626100
H 1.46810500 1.39801100 -2.33936100
H 3.64967000 1.14912900 -3.51055100
H 5.24543700 -0.62307300 -2.72026900
H 4.59588700 -2.07029600 -0.81640600
H -0.60257200 -1.95567600 2.32441400
H 0.58940600 -3.80633100 3.48729000
H 2.88923300 -4.43937500 2.69781500
H 3.89862600 -3.20159400 0.80262900
C -2.32028900 -1.74565100 -0.56483800
C -0.55584000 -2.21769600 -2.02451800
C -1.30652000 -3.17637700 -2.68527700
C -2.60648900 -3.41656800 -2.25820900
C -3.11930000 -2.69599200 -1.18741900
C -2.75072300 -0.92238000 0.56877500
C -2.12891100 0.78701500 2.03773500
C -3.34449400 0.71430600 2.69808100
C -4.28575500 -0.21122300 2.26492000
C -3.98797000 -1.03749300 1.18944000
H 0.46575600 -1.98998500 -2.32352700
H -0.87057900 -3.71741000 -3.51964300
H -3.22261000 -4.16115900 -2.75551300
H -4.13509000 -2.86986600 -0.84514300
H -1.35974700 1.49458500 2.34178000
H -3.53933300 1.37654500 3.53617800
H -5.24909700 -0.29360500 2.76161900
H -4.71148900 -1.76938600 0.84226400
C 0.56917800 2.84253400 0.56577500
C 1.09388700 3.97037400 1.18390000
C 1.96082300 3.81392300 2.25755200
C 2.28992600 2.53585300 2.69161800
C 1.74295300 1.44780400 2.03139600
C -0.36500600 2.87745900 -0.56279200
C -0.81175300 4.04281000 -1.17309500
C -1.69462800 3.95260100 -2.24152200
C -2.11591700 2.70247400 -2.67832600
C -1.64116800 1.57559300 -2.02759700
H 0.82762500 4.96366300 0.83528500
H 2.37502600 4.68894900 2.75172900
H 2.96161000 2.37269400 3.52898400
H 1.97075500 0.42745200 2.33378600
H -0.47338800 5.01341600 -0.82245300
H -2.04963600 4.85677100 -2.72918200
H -2.80374700 2.59091600 -3.51104400
H -1.94052800 0.57452700 -2.33289500
N -1.84072600 -0.01288300 1.00050500
N -1.05344500 -1.52062800 -0.99315500
N 0.94428800 -1.59451000 0.99198200
N 1.83762700 -0.14475500 -1.00260700
N 0.90379300 1.60033200 0.99681200
N -0.78594400 1.66363000 -0.99864700
$end
$rem
JOBTYPE opt
EXCHANGE CAM-B3LYP
CIS_N_ROOTS 40
CIS_SINGLETS true
CIS_TRIPLETS false
CIS_STATE_DERIV 28
STATE_FOLLOW TRUE
FOLLOW_ENERGY 1000000
FOLLOW_OVERLAP 90
NTO_PAIRS 2
BASIS def2-svp
ECP def2-ecp
XC_GRID 3
SOLVENT_METHOD pcm
THRESH 12
MEM_TOTAL 50000
MAX_SCF_CYCLES 1500
GUI 2
$end
$pcm
Theory CPCM
Method SWIG
Solver Inversion
Radii Bondi
$end
$solvent
Dielectric 78.39
OpticalDielectric 1.777849
$end
$van_der_waals
1
44 2.02
$end